EP0302665A1 - Homogene partielle Oxydation eines methanhaltigen Paraffinkohlenwasserstoffes - Google Patents

Homogene partielle Oxydation eines methanhaltigen Paraffinkohlenwasserstoffes Download PDF

Info

Publication number
EP0302665A1
EP0302665A1 EP88306982A EP88306982A EP0302665A1 EP 0302665 A1 EP0302665 A1 EP 0302665A1 EP 88306982 A EP88306982 A EP 88306982A EP 88306982 A EP88306982 A EP 88306982A EP 0302665 A1 EP0302665 A1 EP 0302665A1
Authority
EP
European Patent Office
Prior art keywords
process according
methane
reaction
feedstock
oxygen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP88306982A
Other languages
English (en)
French (fr)
Other versions
EP0302665B1 (de
Inventor
Mark Julian The British Petr. Comp. P.L.C. Howard
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BP PLC
PetroIneos Europe Ltd
Original Assignee
BP PLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BP PLC filed Critical BP PLC
Publication of EP0302665A1 publication Critical patent/EP0302665A1/de
Application granted granted Critical
Publication of EP0302665B1 publication Critical patent/EP0302665B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/909—Heat considerations
    • Y10S585/91—Exploiting or conserving heat of quenching, reaction, or regeneration
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/909—Heat considerations
    • Y10S585/911—Heat considerations introducing, maintaining, or removing heat by atypical procedure
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/929—Special chemical considerations
    • Y10S585/943—Synthesis from methane or inorganic carbon source, e.g. coal

Definitions

  • the present invention relates in general to the homogeneous partial oxidation of a methane-containing paraffinic hydrocarbon feedstock and in particular to operation of the process in a manner whereby C2 and higher hydrocarbons, for example ethylene, are produced.
  • Partial oxidation of methane in premixed methane/oxygen mixtures at high pressure, for example greater than 20 bar, is known for the production of partial oxygenates, principally comprising methanol and formaldehyde.
  • US Patent No. 4,618,732 discloses a process for converting natural gas containing methane to methanol, comprising: thoroughly and intimately mixing natural gas with gaseous air or oxygen to achieve substantially complete homogeneity of these gases; feeding the resulting gas mixture to an inert reactor under elevated pressure, said reactor having an internal surface surrounding a zone in which said gases react, said surface being made of a material selected from the group consisting of glass, non-reactive plastics, non-reactive waxes and non-reactive salts; and reacting said gases in said reaction zone at an elevated temperature in the absence in said reaction zone of any added material which measurably affects the rate of selectivity of the reaction or the yield of product.
  • the co-products of this type of reaction are principally carbon dioxide and water.
  • the present invention provides a process for the production of a C2 and higher hydrocarbons product including ethylene from a methane-containing gaseous paraffinic hydrocarbon feedstock which process comprises heating under elevated pressure in a pre-heating zone a mixture of the feedstock and oxygen in an amount of at least 5% mol to a temperature sufficient to cause spontaneous reaction, the pre-heating and mixing being effected in a manner such that (i) substantial oxygen consumption is avoided, and (ii) a "flash-back" of the reaction to form a diffusion flame at the point of gaseous mixing is prevented, and thereafter in a reaction zone allowing the feedstock mixture to spontaneously react.
  • An advantage of the process of the invention as hereinbefore described is that it can be operated in a manner which does not produce significant quantities of acetylene, which is difficult to quench. A quench step can be avoided.
  • the product of the process is C2 and higher hydrocarbons comprising a substantial proportion of ethylene. In addition there is formed substantial amounts of carbon monoxide and hydrogen, which are themselves valuable products.
  • the methane-containing gaseous paraffinic hydrocarbon feedstock may be substantially pure methane or it may be methane in combination with one or more other gaseous paraffinic hydrocarbons, for example ethane, propane or butane.
  • a particularly preferred feedstock is natural gas, the composition of which depends upon its origin, but generally principally comprises methane, with varying proportions of ethane, propane and butane.
  • Natural gas containing sulphur is preferably desulphurised before use as a feedstock.
  • the methane-containing feedstock may also contain inert gases, for example nitrogen.
  • Other cofeeds for example hydrogen, carbon monoxide, carbon dioxide or steam, may also be used if so desired.
  • the oxygen used in the performance of the invention may be molecular oxygen, air or oxygen-enriched air. It is preferred to use oxygen either in pure form or containing minor proportions of inert gases, for example nitrogen. Preferably oxygen is present in an amount of greater than 10% mol.
  • Pre-heating in a manner such that (i) substantial oxygen consumption is avoided, and (ii) a "flash-back" of the reaction to form a diffusion flame at the point of gaseous mixing is prevented may suitably be accomplished by mixing the methane-containing gaseous paraffinic hydrocarbon feedstock and oxygen at ambient temperature, and then rapidly heating to the spontaneous reaction temperature in a region wherein the gas velocity exceeds the propagation velocity of the reaction.
  • mixing and preheating may be accomplished simultaneously by the incremental addition of oxygen to hydrocarbon gas flowing through an externally heated region. This region may be empty, but the velocity of the gas flowing therethrough may be sufficiently high to prevent reaction. Alternatively, it may contain a packed bed of inert material.
  • the packed bed may suitably be comprised of a granular or powdered material capable of preventing flame propagation and slower oxidation reactions occurring to a significant extent.
  • a wide range of materials may suitably perform this function, for example fused alumina granules which may either be clean or washed with potassium chloride solution or zirconia powder, suitably of a particle size in the range from 400 to 850 microns.
  • Other materials which may be employed include fused silica, magnesia, and the like, which may be treated with substances such as potassium chloride or lead oxide.
  • the elevated pressure at which the mixture of gases is heated is preferably greater than 20 bar.
  • the temperature sufficient to cause spontaneous reaction of the gaseous mixture will to some extent depend on the composition of the mixture but will generally be at least 400°C.
  • the gaseous mixture at, or above, the point of spontaneous ignition is passed to the reaction zone wherein it is allowed to spontaneously ignite.
  • a spontaneous homogeneous reaction occurs which consumes the available oxygen. during the reaction the gas temperature rises rapidly to a value dependent upon the initial oxygen content (typically greater than 800°C).
  • the product selectivity to C2+ hydrocarbons may exceed 40% C mol, whilst the hydrogen/carbon monoxide ratio generally exceeds 1.0. Conversion generally exceeds 15%, and is limited only by the reaction temperatures that can be tolerated by the apparatus and the effectiveness of the inhibition during preheat. Maximum preheat levels are desirable.
  • the reaction zone is preferably maintained under adiabatic conditions.
  • reaction zone should be fabricated in a material capable of withstanding high temperatures, for example up to 1200°C.
  • the product resulting from operation of the process of the invention may be separated into its individual components or may be reacted together in a subsequent synthesis reactor to produce, for example, carbonylated products.
  • 1 is a 9mm internal diameter stainless steel tube
  • 2 is a mixing and pre-heating zone enclosed within a furnace (not shown)
  • 3 is an oxygen injector consisting of a tube closed at the end within the tube 1 and having 10 holes (0.1 mm) 4 evenly spaced along the tube
  • 5 is a reaction zone.
  • 6 is a packing of fused alumina granules
  • 7 is a glass wool plug.
  • 8 is a stainless steel tube liner.
  • methane/nitrogen mixtures were fed to the tube 1 and passed through a packed bed approximately 30 cm long of fused alumina granules 6 heated by an external furnace (not shown).
  • the portion of the tube 1 within the furnace constituted the mixing and pre-heating zone 2.
  • Oxygen was fed through the oxygen injector 3 and passed through the holes 4 into the methane/nitrogen mixture flowing through the tube 1, thereby mixing in a staged manner with the methane/nitrogen mixture and simultaneously being progressively heated.
  • the pre-mixed and pre-heated gas was allowed to spontaneously ignite in the reaction zone 5.
  • the glass wool plug 7 was present to minimise the escape of fused alumina granules.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP88306982A 1987-08-05 1988-07-28 Homogene partielle Oxydation eines methanhaltigen Paraffinkohlenwasserstoffes Expired - Lifetime EP0302665B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB878718488A GB8718488D0 (en) 1987-08-05 1987-08-05 Chemical process
GB8718488 1987-08-05

Publications (2)

Publication Number Publication Date
EP0302665A1 true EP0302665A1 (de) 1989-02-08
EP0302665B1 EP0302665B1 (de) 1992-03-18

Family

ID=10621828

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88306982A Expired - Lifetime EP0302665B1 (de) 1987-08-05 1988-07-28 Homogene partielle Oxydation eines methanhaltigen Paraffinkohlenwasserstoffes

Country Status (12)

Country Link
US (1) US5026946A (de)
EP (1) EP0302665B1 (de)
JP (1) JPS6450828A (de)
CN (1) CN1018731B (de)
AU (1) AU605894B2 (de)
CA (1) CA1304418C (de)
DE (1) DE3869267D1 (de)
GB (1) GB8718488D0 (de)
MY (1) MY103324A (de)
NO (1) NO174744C (de)
NZ (1) NZ225567A (de)
ZA (1) ZA885742B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11485691B1 (en) 2021-04-29 2022-11-01 Totalenergies Onetech Non-catalytic oxidative coupling of methane

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2624115B1 (fr) * 1987-12-03 1990-04-13 Gaz De France Procede et appareil pour la conversion des hydrocarbures
US5270016A (en) * 1990-05-17 1993-12-14 Institut Francais Du Petrole Apparatus for the thermal conversion of methane
DE60036582T2 (de) * 1999-08-06 2008-06-26 Puricore International Ltd. Elektrochemische Behandlung einer wässrigen Lösung
US20070051640A1 (en) * 2000-08-07 2007-03-08 Sterilox Technologies, Inc. Electrochemical treatment of an aqueous solution
FI118612B (fi) * 2002-11-06 2008-01-15 Nokia Corp Menetelmä ja järjestelmä laskuoperaatioiden suorittamiseksi ja laite
FI118654B (fi) * 2002-11-06 2008-01-31 Nokia Corp Menetelmä ja järjestelmä laskuoperaatioiden suorittamiseksi ja laite
EP1930069B1 (de) * 2006-12-09 2010-09-15 Haldor Topsoe A/S Verfahren und Vorrichtung zum Mischen zweier oder mehrerer Fluidströme
CN111747806B (zh) * 2019-03-27 2023-04-07 中国石油化工股份有限公司 一种防止氧化偶联工艺产生回火的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1978621A (en) * 1930-06-11 1934-10-30 Doherty Res Co Process for partial oxidation of hydrocarbons and the like
GB818395A (en) * 1955-06-21 1959-08-19 Union Carbide Corp Improvements in or relating to apparatus for the partial oxidation of hydrocarbons
WO1985000164A1 (en) * 1983-06-20 1985-01-17 Exxon Research And Engineering Company High temperature production of benzene from natural gas
EP0178853A2 (de) * 1984-10-18 1986-04-23 The British Petroleum Company p.l.c. Konvertierungsverfahren

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2672488A (en) * 1949-05-05 1954-03-16 Phillips Petroleum Co Partial oxidation of hydrocarbons
US2726276A (en) * 1951-03-26 1955-12-06 Union Oil Co Acetylene-making process
US2679542A (en) * 1951-04-09 1954-05-25 Union Oil Co Process for the production of acetylene
US2679543A (en) * 1951-05-14 1954-05-25 Union Oil Co Production of acetylene
US2713601A (en) * 1951-07-28 1955-07-19 Union Oil Co Production of acetylene
US2905731A (en) * 1955-07-25 1959-09-22 Phillips Petroleum Co Hydrocarbon conversion method
GB929136A (en) * 1960-09-12 1963-06-19 Toyo Koatsu Ind Inc Improvements in or relating to the production of acetylene and ethylene

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1978621A (en) * 1930-06-11 1934-10-30 Doherty Res Co Process for partial oxidation of hydrocarbons and the like
GB818395A (en) * 1955-06-21 1959-08-19 Union Carbide Corp Improvements in or relating to apparatus for the partial oxidation of hydrocarbons
WO1985000164A1 (en) * 1983-06-20 1985-01-17 Exxon Research And Engineering Company High temperature production of benzene from natural gas
EP0178853A2 (de) * 1984-10-18 1986-04-23 The British Petroleum Company p.l.c. Konvertierungsverfahren

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Journal of the Chemical Society, Chemical Communications, No. 17, 1987 KENJI ASAMI et al. "Oxidative Coupling of Methane in the Homogeneous Gas Phase under Pressure" pages 1287, 1288 * Totality * *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11485691B1 (en) 2021-04-29 2022-11-01 Totalenergies Onetech Non-catalytic oxidative coupling of methane
EP4082996A1 (de) 2021-04-29 2022-11-02 TotalEnergies OneTech Nichtkatalytische oxidative kupplung von methan

Also Published As

Publication number Publication date
CA1304418C (en) 1992-06-30
CN1018731B (zh) 1992-10-21
NO883467L (no) 1989-02-06
EP0302665B1 (de) 1992-03-18
AU2029088A (en) 1989-02-09
NO883467D0 (no) 1988-08-04
NO174744C (no) 1994-06-29
ZA885742B (en) 1990-04-25
AU605894B2 (en) 1991-01-24
DE3869267D1 (de) 1992-04-23
US5026946A (en) 1991-06-25
NO174744B (no) 1994-03-21
CN1032156A (zh) 1989-04-05
JPS6450828A (en) 1989-02-27
GB8718488D0 (en) 1987-09-09
MY103324A (en) 1993-05-29
NZ225567A (en) 1990-10-26

Similar Documents

Publication Publication Date Title
CA2097435C (en) Process for the production of ethylene and mixtures containing ethylene
US4726913A (en) Conversion process
JP3190129B2 (ja) モノオレフィンの製造方法
US4758375A (en) Conversion process
NO995207L (no) Fluidisert sjikt-prosess og anordning for fremstilling av syntesegass
EP0302665A1 (de) Homogene partielle Oxydation eines methanhaltigen Paraffinkohlenwasserstoffes
US4048091A (en) Process for the preparation of reducing gases
US3967936A (en) Methanation process utilizing split cold gas recycle
US4767569A (en) Process for producing synthesis gas by partial combustion of hydrocarbons
US4714796A (en) Production of higher molecular weight hydrocarbons from methane
US3644555A (en) Process for the production of acetylene or acetylene and ethylene by pyrolysis of hydrocarbons
JP2002147720A (ja) 部分酸化法用予備混合バーナブロック
US1965770A (en) Production of acetylene
DE2352438A1 (de) Verfahren zur katalytischen teiloxydation von kohlenwasserstoffen
US4321131A (en) Process for heat carrier generation
US3468641A (en) Conversion of liquid hydrocarbons into fuel gas or water gas by a thermal or catalytic splitting
US4854943A (en) Process of producing a gas which is rich in carbon monoxide by a cracking of hydrocarbons
AU682751B2 (en) Synthesis gas preparation by partial oxidation-steam reforming
US3738940A (en) Method of operating a burner for the partial oxidation of hydrocarbons to synthesis gas
US3161695A (en) Process for making acetylene
US4983783A (en) Reduction in carbon oxides in oxidative pyrolysis of halogenated methanes
US4758249A (en) Hydrogen reduction of carbonaceous source to form carbon monoxide
US3116343A (en) Temperature-stabilized conversion of hydrocarbons and the like
US2992075A (en) Preparation of carbon black
GB1028028A (en) Thermal conversion process and apparatus therefor

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE FR GB IT NL

17P Request for examination filed

Effective date: 19890616

17Q First examination report despatched

Effective date: 19910215

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB IT NL

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

REF Corresponds to:

Ref document number: 3869267

Country of ref document: DE

Date of ref document: 19920423

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

NLS Nl: assignments of ep-patents

Owner name: O&D TRADING LIMITED

Effective date: 20070323

NLT1 Nl: modifications of names registered in virtue of documents presented to the patent office pursuant to art. 16 a, paragraph 1

Owner name: BP P.L.C.

Owner name: INEOS EUROPE LIMITED

Owner name: INNOVENE EUROPE LIMITED

Owner name: BP AMOCO P.L.C.

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20070831

Year of fee payment: 20

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

Ref country code: FR

Ref legal event code: CA

Ref country code: FR

Ref legal event code: CD

BECA Be: change of holder's address

Owner name: *INEOS EUROPE LTDHAWKSLEASE, CHAPEL LANE, LYNDHURS

Effective date: 20070202

BECH Be: change of holder

Owner name: *INEOS EUROPE LTD

Effective date: 20070202

BECN Be: change of holder's name

Owner name: *INEOS EUROPE LTD

Effective date: 20070202

Owner name: *INEOS EUROPE LTDHAWKSLEASE, CHAPEL LANE, LYNDHURS

Effective date: 20070202

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20070727

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20070816

Year of fee payment: 20

Ref country code: NL

Payment date: 20070724

Year of fee payment: 20

Ref country code: IT

Payment date: 20070730

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20070717

Year of fee payment: 20

BE20 Be: patent expired

Owner name: *INEOS EUROPE LTD

Effective date: 20080728

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20080727

NLV7 Nl: ceased due to reaching the maximum lifetime of a patent

Effective date: 20080728

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20080728

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20080727